Resinous product and process of making same



Patented Oct. 2, 1934 RESINOUS PRODUCT AND PROCESS OF I MAKING SAME Joseph V. Meigs, Dobbs Ferry, N. Y., assignor to Plastix Corporation, Wilmington, DeL, a corporation of Delaware No Drawing. Application July 14, 1 932,

1 Serial No, 622,457 7 9 Claims. (01. 260-2) This invention relates to artificial resins, espeamples of the latter group, the oxides or hydroxcially to carbohydrate-phenol resins and intended ides of calcium, barium, aluminum, lead, zinc, tin, for use in the manufacture of molded or pressed manganese, etc. I may, however, use any metallic articles, impregnated substances or structures, compound which will be sufiiciently reactive to or varnishes, or for other purposes for which bring about one or more of the improvements products of this general type are used. herein noted, although I prefer to use metallic One of the objects of the invention is to procompounds not freely soluble in water. vide resinous products possessing mechanical The invention in its preferred form may be strength of a high order together with an inpracticed by reacting afusible carbohydrate phe- 10 creased resistance to water and improved elecnol resin with a difficultly water soluble metallic trical insulating properties under conditions inbasic body and a formaldehyde derivative, as for volving the presence of Water. Another object is example, hexamethylene tetramine. The mutual to increase the speed with which such resins action of the methylene amine and the metallic may be hardened or rendered infusible. These compound produces surprising improvements, the 15 and other objects will be more fully hereinafter resulting product possessing electrical insulating described. properties much superior, especially under con- In the preferred form of the present invention ditions involving moisture, to those characteris- I use the primary resins, that is the resins at tic of the same resin acted on by the formaldethe soluble and fusible stage, madeas described hyde derivative in the absence of the metallic ,20 in my U. S. Patent No. 1,593,342, issued July 20, basic compound. 7 1926, U. S. Patent No. 1,868,215, issued July 19, In atypical case, the insulation resistance of 1932; although I may u other r as for an infusible resinous product made by heating example, the primary resins described in ,U. S. 'a mixture of carbohydrate phenol resin, wood Pa nt o. issued ua y 3 flour and hexamethylene tetramine was increased 25 U. S. Patent N0. 1,832,038, issued November 17, approximately ten fold by including a substan- 1931,- U- Patent 1,391,052, issued April tial proportion of calcium hydroxide in the com- .1931, or U. S. Patent No. 1,801,053, issued April position. In the instance referred to the value 14, 1-931; fusible and Soluble, bohyd at of the insulation resistance was measured after p l resins incorporating fatty a ds r ils, exposing the product to a humidity of' 90 per 30 as described in my'U. S. Patent No. 1,868,216, cent for five, days and therefore constitutes a issued July 19, 1932. a measure of the ability of the resinous product In Carrying out the v ntion in its preferred to withstand the action of moisture. At the f rm, I s ct a at ve y t us cerbosame time, the value of the product as-a dielechydrate'phenol resin d treat it W t a ui tric insulating medium, measured in terms of 35 able proportion of a reactive metallic basic body, dielectric constant and phase angle difference,

' a for eXample,v five '5 y-fi D cent by was improved more than one hundred per cent.

Weight of Calcium hydroxide and eCl y Hexamethylene tetramine is an efiicient hard- W p t0 Subsequent, to this treatment ening agent for carbohydrate phenol resins in I in orp a a sufiieient p p t of ardthe sense that it yields under suitable conditions 40 ening agent, pr fer ly formaldehyde rivaproducts possessing a high orderof mechanical tive thereof, to enable such resin to become infust th, b t h th disadvantage th t 11-, al ible and mechanically Strong when heated. SuD- produces products which are more susceptible to p ti a xt nd ns or er material a' d s Water than is desired and which do not, parable character may be incorporated at anyisllitticularly under conditions involving moisture,

45 able. stage of the process by various means known possess as high a degree of electrical insulating in'the art. Suc material may be fi 0 1 value as desired for some uses; This disadvanla'l, a Q P Crystalline n Character 7 tage of hexamethylene tetramine, when applied The metallic basic bodies used in the present to carbohydrate phenol resins, is due, in my opininvention may be divided into two broad classes, ion, to the presence in such resins oforganic 50 V 1; e' y Soluble in Wate a d t e 017 acids, probably humic acids or derivatives therefreely soluble or insoluble. The former class of, which are capable of reacting with hexa, or includes"'thehydroxides of the alkali metals the ammonia therefrom, to form water soluble and the latter 'group embraces compounds of or water decomposable products. The deleterithe alkalineearth metals, the earth metals and ous efiect of ammonia on carbohydrate phenol 55 the so-called heavy metals. I may use, as exresins is readily demonstrated by actual test as described in my copending application Serial No. 161,469 filed January 15, 1927, now U. S. Patent No. 1,923,321, issued Aug. 22, 1933.

I have, however, overcome this disadvantage by using a metallic compound in conjunction with hexa, and find that this combination imparts not only suitable mechanical strength but also electrical insulating value and Water resistance of a high order.

A possible explanation of the benefits thus obtained is that those constituents of the resin Which otherwise react with ammonia (or hexamethylene tetra-mine) may first react. with the metallic base and thus become inert toward ammonia, or, the metallic base may liberate ammonia from its union with the resin. Itis also possible that the water soluble or water-decomposable. reaction products of the resin and ammonia (or hexamethylene tetramine) may forrn a water insoluble addition product of a physicochemical character or a chemical character with the metallic base. Any of these or equivalent effects are to be understood as meant by the term derivative employed in the claims. My observations appear to indicate that electrical insulating value and water resistance are highest when the quantity of metallic base is at least approximately chemically equivalent to the ammonia capable of being yielded by the hexamethylene tetramine.

The advantages accruing to the use of a metallic compound in conjunction with a methylene amine as described may be noted by reference to the following table, which refers to mold ed compositions containing resin, wood fiour and hardening agent. In one case hexa is used in conjunction with calcium hydroxide; in theother hexamethylene tetramine alone is used.

Table No. 1 No. 2

Composition Composition with with hexamethhexamethylene ylene tetratetramlne and mine and 0211- without calcium cium hydroxide hydroxide Insulation resistance...

Dielectric constant Phase angle difference (at 1,000

cycles).

Product of dieletric constant multiplied by phase angle difference.

Transverse breaking strength in pounds per square inch of cross section.

319 to 525 meg- 40 megohms (or 01 less).

3.0 4.1. 2.0 degrees 3.5 degrees.

It Will be seen that the composition using calcium hydroxide is vastly superior in magnitude of insulation resistance to the composition without the metallic base. With respect to dielectric properties, since the product of phase .angle difobservations, this bleaching effect appears to be due to a mutual action of the reactive metallic compound, and the methylene amine, or amm inia, on the resin. This is an important discovery in View of the demand for molded or pressed products with colors other than black.

Still another advantage due to the combined use of a metallic compound and a hardening agent, particularly a methylene hardening agent, as applied to a carbohydrate phenol resin, is an increase in the rate of curing (hardening). The metallic compound appears to activate the methylene compound. This has been observed in particular in the case of hexa when used with lime.

The invention may be practiced in various ways. For example: (1) A fusible resin may be mixed with a metallic base, an aldehydic or methylene hardening agent such as the methylene amine, hexamethylene tetramine, and filling material, first in a ball mill and subsequently on heated rolls. (2) A solution of the resin in a solvent such as alcohol may be mixed with a hardening agent, metallic base and filling material and the solvent then evaporated or distilled. (3) The resin may be heated with a metallic base until th latter combines, in whole or in part,

with the resin; and the resulting product then mixed with the hardening agent, and with the filling material, if used, either by the'dry method, or by'using a solvent. Other modifications Will suggest themselves to those skilled in the resin art. Such procedures will yield compounds suitable for molding. The filling material is generally of a comminuted nature and often cellular or fibrous, such as wood flour, cotton flock, or other forms of cellulose.

Impregnated or coated paper or fabric is prepared by substantially the same method, the filling material being, however, in sheet form instead of in a comminuted condition. This diiference necessitates a somewhat different technique in applying the resin to the filling material. It is possible to heat the resin with a suitable metallic compound, dissolve such product in a volatile solvent, together with the hardening agent, as

for example hexa, and then use the resulting varnish as an impregnating or coating medium for application to paper or fabric. Equivalent results might be obtained by preparing a paper or fabric loaded with suitable proportions of metallic base, and then impregnating or coating such paper or fabric with a solution of resin containing an appropriate hardening agent.

For the preparation of molding material one may proceed in a typical case as follows:

Example 1 4 In a ball mill pulverize and grind together 1000 grams of a primary carbohydrate phenol resin, such as the primary or soluble: and fusible resins described in Patent No. 1,593,342, together with 120 grams of calcium hydroxide and 150 grams of desired and mold at a temperature of 150 to 180 degrees centigradeunder pressure in the mamier customary for hot molded or heat-set products.

I am not limited to the precise proportions of metallic compound indicated. The proportions specifically described herein are for illustrative purposes only. Some carbohydrate phenol resins may contain free sulphuric acid or other equivalentsubstance used as a converting agent in the reaction between carbohydrate and phenol, and in such case I use more than enough metallic compound to react with such acid converting agent. When the hardening agent is amethylene amine, I may, asv already described'advantageously use sufiicient metallic compound to be chemically equivalent to the ammonia or amine capable of being yielded by such hardening agent. Nor am I limited to any particular metallic'compound. I have obtained good results by using the more dificultly water soluble metallic hydroxides or corresponding oxides, but I may use any metallic compound sufficiently basic or reactive to effect the improvements herein described. In some cases I can use the metallic salts of fatty acids.

I am aware of proposals to neutralize mineral acid catalysts in phenolic resins by bases including metallic bases and then to heat the product with a formaldehyde derivative, and wish to point out that my invention is quite different. In such procedures the mineral acid is converted into a metallic derivative but the organic resinous constituents are unaffected. My object is to have enough reactive basic compound to form a derivative with certain organic constituents of the resin and the methylene amine hardening agent. In my method, the neutralization of any mineral acid which may be present is merely incidental.

The condensation product of ammonia and formaldehyde known as hexamethylene tetramine is the hardening agent I prefer, but the invention is not restricted thereto, as I may use any other suitable hardener, such as trioxymethylene, condensation products of formaldehyde and aromatic amines, and other compounds, which in conjunction with a metallic base, act on carbohydrate phenol resins to produce products possessing mechanical strength of a high order coupled with superior resistance to water and improved electrical insulating properties, as herein described.

The property herein described as insulation resistance was determined in the following manner:

The samples were 12.5 centimeters long, 1.3 centimeters wide and 1.3 centimeters thick. Brass strips wrapped with tinfoil were used as electrodes. Each electrode consisted of two strips between which the sample was clamped. Two

.such electrodes were placed on each sample 2.6

centimeters apart. The tinfoi1 along the edge of each electrode was pressed down against the surface of the sample with the dull edge of a knife in order to insure good contact with the surface. The samples were placed in a humidity chamber in which the relative humidity was kept constant at per cent humidity by means of a sulphuric acid mixture of the proper specific gravity. At the end of five days, measurements of the electrical resistance between the electrodes on each sample were made. The results were reported in megohms and are the resistances in megohms between the two electrodes as described.

The term high insulation resistance is a relative one and refers to the improvements as herein described. The same thing is true of the term water resistant. The term mechanical strength of a high order refers to values for modulus of rupture or transverse breaking strength in the neighborhood of 8000 pounds per square inch or more.

I have found that glycerine may be used as hardening agent for carbohydrate phenol resins. I have reacted glycerine with such resins and thereby changed fusible resins to the infusible state. The following example may be cited as an illustration.

carbohydrate phenol resin of the type referred to asa primary resin'in Example 1, was distilled until the temperature of the resin reached 230 degrees'centigrade. Free phenol was evolved and condensed. To the residue, about 16 per cent by weight of glycerine on the weight of the primary resin was added and distillation continned, the temperature of the mass rising from 214 to'260 degrees centigrade during about two and one half hours. At the end of this time the resin became infusible and resilient.

Calcium hydroxide, or other equivalent, may be incorporated in the above composition in the same manner set forth in Example 1 and with similar beneficial results. Likewise, in some cases it is found desirable to employ in addition to the glycerine varying amounts of methylene hardening agents such as hexamethylene tetramine.

The slow rate of hardening noted in Example 2 suggests the application of this reaction in the production of resinous products that are molded and subsequently baked to harden, i. e. in the cold molding art. In such application, the glycerine or equivalent will act as a flux for the molding operation and as a hardening agent in the subsequent baking. As is well known in the cold molding art, the molding mixtures should be plastic during molding and it is desirable that plasticizing agents combine chemically during the subsequent baking. It would appear that glycerine may perform these functions.

While my invention in its preferred form involves the use of a metallic base in conjunction with a methylene hardening agent, I may in some cases, especially with resinous products the properties of which do not require the use of such hardening agent, dispense with the employment of the same. The following example is an illustration. In this example aniline with hydrochloric acid is used as a converting agent and it is to be understood that other converting agents may be employed as for example sulphuric acid.

Example 3 A reaction mixture consisting of Argo corn sugar (crude dextrose) 420 grams, meta-para cresol 180 com., water 100 cubic centimeters, aniline 30 cubic centimeters, and concentrated hydrochloric acid 8 cubic centimeters was boiled under 2. reflux condenser for five hours, the reflux condenser being cooled by a flow of cool water at ordinary temperature. a resinous product were formed. The latter was removed and washed with hot water. 1 5 grams of lead dioxide were incorporated with the washed resinous product, without dehydrating the latter, and the resulting mass heated. At about 140 degrees F. there was a sudden coagulation. Water separated and a tough rubbery mass was produced.

This application is a continuation in part of mycopending application Ser. No. 232,459 filed November 10, 1927.

What I claim is:

1. The process of making a resinous substance which comprises heating a primary carbohydrate phenol resin to approximately 230 0., adding An aqueous solution and approximately 16% by Weight of glyc-erine on the Weight of the primary resin, and continuing the application of heat until the substance be- GtThe reabti'on prcd'uet of a carbohydrate phenol resin, glycerin'e and calcium hydroxide;

7; The reaction product of a carbohydrate phenol resin; glyeerine, a methylene hardening agent and a compound of the group consisting of oxides and hydroxides of metals.

The reaction product of a carbohydrate phenol resin, gly'ce'riri'e, a methylene amine hardening agent and a compound of the group consisting of alkaline reacting oxides and hy dioxides of metals. I

9. The reaction product of a carbohydrate phenol resin, 'glycerine, hexamethylene tetramine and a compound of the group consisting of alka line reacting oxides and hydroxides of metals.-

' V JOSEPH VJMEIGS. 

